CN101479104A - Rigid optical laminates and methods of forming the same - Google Patents
Rigid optical laminates and methods of forming the same Download PDFInfo
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- CN101479104A CN101479104A CNA2007800241947A CN200780024194A CN101479104A CN 101479104 A CN101479104 A CN 101479104A CN A2007800241947 A CNA2007800241947 A CN A2007800241947A CN 200780024194 A CN200780024194 A CN 200780024194A CN 101479104 A CN101479104 A CN 101479104A
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/13338—Input devices, e.g. touch panels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2202/00—Materials and properties
- G02F2202/28—Adhesive materials or arrangements
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- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Mathematical Physics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Liquid Crystal (AREA)
Abstract
An optical article and method or forming an optical article are disclosed. The optical article includes a first rigid optical substrate, a second rigid optical substrate, and a self-supporting optical adhesive disposed between the first rigid substrate and the second rigid substrate. The self-supporting optical adhesive includes a cross-linked silicone based polymer network and a silicone fluid disposed in the polymer network.
Description
Background technology
The present invention relates generally to rigid optical laminates and forming method thereof.
Optical goods are formed by rigid optical element usually.These rigid optical element put together usually, and are provided with air gap between two rigid optical element.There is refractive index difference usually in air/rigid optical element interface, and described refractive index difference can cause the optical loss at this air/rigid optical element interface place.
Anti-reflection coating is applied to these air/rigid optical element interface and sentences the reduction optical loss.Yet these coating are expensive usually, and can not eliminate airgap effect fully.
Between rigid optical element, use contact adhesive with rigid optical element laminated each other be the part difficult matter, and can between rigid optical element, cause visible bubble in bubble usually.These bubbles can cause optical loss again.
Summary of the invention
In one exemplary embodiment, the present invention relates to optical goods.These optical goods comprise first rigid optical substrate, second rigid optical substrate and be arranged on first rigid basement and second rigid basement between the optical adhesive of supporting certainly.Comprise based on the polymer network of crosslinking silicone and be arranged on silicone liquid (silicone fluid) in the polymer network from the supporting optical adhesive.
In another exemplary embodiment, the present invention relates to form the method for optical goods.This method comprises: first rigid optical substrate is provided, and it has the optical adhesive layer of supporting certainly of surface and contiguous this surface setting; And second rigid basement is laminated in from supporting on the optical adhesive layer, to form optical goods.Be arranged between first rigid optical substrate and second optical substrate from the supporting optical adhesive layer, and support optical adhesive certainly and comprise based on the polymer network of crosslinking silicone and be arranged on silicone liquid in the polymer network.
By the following specific embodiment also in conjunction with the accompanying drawings, will be conspicuous for the person of ordinary skill of the art according to the optical stack of this theme invention and these and other aspects of liquid crystal display.
Description of drawings
How to prepare and use this theme invention for the those of ordinary skill that makes this theme technical field that the present invention belongs to is more readily understood, describe its exemplary embodiment in detail below in conjunction with accompanying drawing, wherein:
Fig. 1 is the schematic cross sectional views of exemplary optical article; And
Fig. 2 is the schematic cross sectional views of another exemplary optical article.
The specific embodiment
The present invention relates generally to rigid optical laminates and forming method thereof, and relate in particular to from supporting optical adhesive, this supports optical adhesive certainly and comprises based on the polymer network of crosslinking silicone and be at least partially disposed on silicone liquid in the polymer network, to form from the optical adhesive that supports re-binding, it allows rigid optical element each other from laminated.Yet the present invention is not limited, and the discussion by the embodiment that provides below will obtain the understanding to various aspects of the present invention.
It has been found that, as herein describedly can be used as the practical approach of filling air gap from supporting adhesive, this air gap appears between the rigid optical substrate such as (for example) LCD and coating sensor or protection face board usually.These have from wetting ability from supporting adhesive, and allow the rigidity-rigid lamination (rigid-to-rigid lamination) of no air/gas bubbles, and need not high-pressure laminating equipment.These can fill the air gap that is present in usually in the optical goods with adjacent rigid substrate from supporting adhesive, to improve overall optical performance.
From supporting adhesive two rigid basement are laminated to a time-out certainly as herein described, this supports adhesive certainly can make adjacent rigid basement optically-coupled.Use the air gap that supports certainly between adhesive filling rigid optical substrate as herein described, can strengthen transmission and reduce dazzle by eliminating two rigid basement/significant refractive index mismatch in air interface place.In addition, use the air gap that supports certainly between adhesive filling rigid optical substrate as herein described, can exempt the needs that on two rigid basement, apply anti-reflection coating.
As herein describedly can also make a rigid basement have interim or lasting re-binding with respect to other rigid basement from supporting adhesive, this is by peeling off one or two rigid basement to realize from supporting adhesive from as herein described.During two rigid optical substrate durable adhesion that will be such as (for example) LCD and rigidity protecting cover, if the rigidity protecting cover by scratch, damage or assemble improperly, then needs to replace whole LCD.As herein describedly allow these scratches, damage or assemble improperly optical goods as herein describedly to obtain repairing in the mode that only removes rigid basement from supporting adhesive by using from supporting adhesive, if desired, also can use described from support adhesive with the rigid basement substitute from laminated.
Below explanation should read in conjunction with the accompanying drawings, and same element is numbered in the same way in the wherein different accompanying drawings.Accompanying drawing may not be drawn in proportion, and it is depicted as the exemplary embodiment of selection, and is not to be intended to limit the scope of the present disclosure.Though show the example of structure, yardstick and the material of various elements, person of skill in the art will appreciate that the many examples that provided all have available suitable alternative form.
Except as otherwise noted, all numerical value of employed representation feature size, amount and physical property all are interpreted as being limited by term " about " in all cases otherwise in this specification and claims.Therefore, unless opposite indication is arranged, otherwise the numerical parameter of listing in above-mentioned specification and the appended claims is approximation, and according to the desirable characteristics that those skilled in the art utilizes instruction content disclosed herein to seek to obtain, these approximations can change.
Number range by the end points statement comprises all numerical value (for example, 1 to 5 comprises 1,1.5,2,2.75,3,3.80,4 and 5) and any scope in this scope that comprises in this scope.
In this specification and the appended claims, the singulative of use " ", " one ", " being somebody's turn to do ", " described " or the situation that does not indicate quantity comprise that referent is more than one situation, unless described content is clearly indicated other implications.Comprise when for example, mentioning " a slice film " have a slice, two or the situation of multi-disc film more.The term that uses in this specification and the appended claims " or " implication generally include " and/or ", unless described content is indicated other implications clearly.
Term " polymer " " be understood to include polymer, copolymer (as the polymer that uses two or more different monomers to form), oligomer and their combination.
Term " optical thin film " or " optical substrate " refer to film or the substrate used in the optical application.Optical application comprises (for example) window film, optical display.These films or substrate control are by their light.
Term " rigid basement " is meant unbending single or multiple lift substrate.For example, rigid basement is being removed Shi Buhui formation " peeling off cutting edge of a knife or a sword " (peelfront) according to peel adhesion test method.In a plurality of embodiment, rigid basement can not be to be enough to implement the mode generation elastic bending of peel adhesion test method (needs at least 45 degree are crooked usually).An example of rigid basement is the glassy layer with a millimeter or bigger thickness.Panel of LCD is the examples of articles that comprises rigid basement.Rigid basement also can be formed by the layer flexible layer, and this layer flexible layer is laminated together in a certain way becoming rigid body, but the multilayer rigid basement can comprise the rigid layer as one of multilayer usually.
Fig. 1 is the schematic cross sectional views of exemplary optical article 100.These optical goods 100 comprise first rigid optical substrate 110, second rigid optical substrate 120 and be arranged on first rigid basement 110 and second rigid basement 120 between the optical adhesive of supporting certainly 130.Comprise based on the polymer network of crosslinking silicone and be at least partially disposed on silicone liquid in the polymer network from supporting optical adhesive 130.
This supporting optical adhesive 130 shows quick humidification power between rigid optical substrate 110,120 certainly, and can form the laminated thing of no air/gas bubbles.In a plurality of embodiment, these remove from supporting optical adhesive 130 with allowing noresidue.In a plurality of embodiment, these are from supporting optical adhesive 130 re-binding enduringly, remove after a while allowing.These can promote the whole surface of wetting front by rigid optical substrate from supporting optical adhesive 130, and need not to apply external pressure (except the gravity).
In certain embodiments, these comprise little science adhesive surface from supporting optical adhesive 130, further describe as follows.Little science adhesive surface can serve as fluid or air discharging channel, and when carrying out the laminated process of zero defect, this passage allows fluid or air from discharging between the rigid optical substrate 110,120.In a plurality of embodiment, little science adhesive surface is out of shape in laminated process adapting with surface characteristics, thereby makes little science adhesive phase distortion.
In a plurality of embodiment, comprise based on the polymer network of crosslinking silicone: silicone polyacrylates; Silicone elastomer, such as (for example), silicone polyurea elastomer or silicone polyoxamide; Or their mixture.
Silicone polyacrylates can be passed through methacryloxy urea siloxanes (methacryloxyurea siloxane) (MAUS-U.S. Patent No. 5, difunctional siloxane acrylate described in 514,730) prepares with vinyl monomer (acrylate that has 8 to 22 carbon atoms such as (for example)) reaction.In a plurality of embodiment, these silicone polyacrylates comprise multifunctional ethylenic unsaturated siloxane polymer, simple function ethylenic unsaturated siloxane macromonomer and vinyl monomer.Available silicone polyacrylates is described in the U.S. Patent application No.11/222284 that is filed on September 8th, 2005 to some extent, and this patent application is incorporated herein in the degree that does not clash.
Have such as (for example) silicone polyurea (as United States Patent (USP) 5,475, described in 124, this patent is incorporated this paper into way of reference) and the radiation-hardenable siloxanes (as United States Patent (USP) 5, described in 214,119, this patent is incorporated this paper into way of reference) and so on the silicone elastomer of polarity part have oxyalkylene segment, this oxyalkylene segment can be assembled in the low-yield surface of adhesive, and forms the rich siloxane surface with low adhesive force.In case these silicone elastomers and another substrate are laminated, oxyalkylene segment can make that As time goes on the adhesive force between adhesive (non-silicone polarity part) and the substrate strengthen from rich siloxanes surface migration.Yet, can make these elastomer crosslinked (as described below) as required so that the enhancing of adhesive force reaches minimum level.Silicone elastomer with polarity part can randomly comprise additive, for example, and plasticizer, antioxidant, ultra-violet stabilizer, dyestuff, pigment, hindered amine as light stabilizer (HALS) etc.
The silicone elastomer that comprises quantity available from the supporting optical adhesive.In a plurality of embodiment, supporting the silicone elastomer that optical adhesive comprises certainly is 20 weight % to 80 weight %.
Silicone polyoxamide elastomers also can be called as the polydiorganosiloxanepolyurea polyoxamide.These elastomers can be linear block copolymers, and this linear block copolymers forms by diamines and the polydiorganosiloxanepolyurea precursors reaction with oxamido-group.In a plurality of embodiment, the polydiorganosiloxanepolyurea polyoxamide block copolymers is (AB)
nType.Available silicone polyoxamide elastomers is described in the U.S. Patent application No.11/317602 that is filed on December 23rd, 2005 to some extent, and this patent application is incorporated herein in the degree that does not clash.
In a plurality of embodiment, add crosslinking agent to these from supporting in the optical adhesive, it is crosslinked that these adhesives are taken place, so that the enhancing of adhesive force reaches minimum level, and produces the stable polymer network with in conjunction with silicone liquid.This crosslinking agent can be any available compatibility crosslinking agent, and such as (for example), heat causes crosslinking agent or radiation-induced crosslinking agent.In crosslinking agent can any available crosslinked amount be included in.In a plurality of embodiment, the amount of the crosslinking agent that comprises in the initial adhesive composition is in the scope of 0.1 weight % to 5 weight %.
Exemplary crosslinking agent comprises free radical curing agent, such as (for example), and organic peroxide and hydroperoxides.Other crosslinking agent comprises light trigger, such as (for example), and benzoin ether, benzophenone and derivative thereof.Other suitable crosslinking agent comprise that those are at U.S. Patent No. 6,369,123 and the U.S. Patent No. 5,407 owned together, the crosslinking agent described in 971.For example γ or electron beam irradiation are realized crosslinked also can to use high energy electromagnetic radiation.
The silicone liquid that comprises quantity available from the supporting optical adhesive.In a plurality of embodiment, supporting the silicone liquid that optical adhesive comprises certainly is 20 weight % to 50 weight %.In a plurality of embodiment, silicone liquid is arranged in the polymer network.Under multiple situation, can be by using general solvent extraction technology to determine whether silicone liquid is set in the polymer network to polymer network.
Available silicone liquid makes this liquid that can not be separated with compatible based on the polymer network of siloxanes.Yet if necessary, those skilled in the art can use general solvent extraction technology usually, and silicone liquid and polymer network are separated.The number-average molecular weight that available silicone liquid has usually is at least about 150 gram/moles, and the number-average molecular weight that more preferably has is at least about 500 gram/moles.In a plurality of embodiment, the molecular weight of this liquid is less than 100,000 gram/moles, or less than about 50,000 gram/moles, or in certain embodiments less than about 30,000 gram/moles.The molecular weight of this liquid can (as GE Silicones, Waterford N.Y.) measures or report by supplier.
In certain embodiments, this liquid is silicone oil.Representational silicone oil includes but not limited to the copolymer of the dimethyl silicone polymer, polyphenyl methyl siloxane, polydialkysiloxane of trialkylsiloxy end-blocking and they and trialkylsiloxy end-blocking material.If desired, can adopt the combination of diversified described liquid.
These liquid can combine with polymer network based on siloxanes by any available method.In certain embodiments, these liquid with based on the polymer network blend of siloxanes, coated then to form from supporting course.In other embodiments, this liquid only is applied to and has formed on surface supporting course, based on the polymer network of siloxanes.This liquid level is distributed to polymer network based on siloxanes in the surface of supporting course.
In other embodiments, this liquid can be arranged on the surface of one or two rigid basement and/or on the surface of supporting course.In these embodiments, also can with this liquid with based on the polymer network blend of siloxanes.Any with based on the described liquid of the polymer network blend of siloxanes all can be applied to rigid basement and/or identical or different from the lip-deep liquid of supporting course.Be coated to rigid basement and/or common at least in part by polymer network absorption based on siloxanes from supporting course from the lip-deep described liquid of supporting course.In a plurality of embodiment, this liquid is silicone liquid (as mentioned above).
First rigid optical substrate 110 and second rigid optical substrate 120 can be formed by any available rigid optical material.In a plurality of embodiment, first rigid optical substrate 110 and second rigid optical substrate 120 can be glass, quartz, sapphire etc., or are polymeric material, such as (for example) Merlon, polymethyl methacrylate (PMMA), polyester etc.
In certain embodiments, second rigid optical substrate 120 forms at least a portion of panel of LCD, and first rigid optical substrate 110 forms at least a portion of clear sensor panel (such as (for example) touch-screen).It has been found that, as herein describedly can be used as the practical approach of filling air gap from supporting adhesive, this air gap appears between the rigid optical substrate such as LCD and coating sensor panel usually.These have uniquely in wettability (as mentioned above) from supporting adhesive, and allow the rigidity-rigid lamination of no air/gas bubbles, and need not high-pressure laminating equipment.These can fill the air gap that is present in usually in the optical goods from supporting adhesive, and these optical goods have adjacent rigid basement.As herein described from support adhesive with two rigid basement when laminated, this supports adhesive certainly can make adjacent rigid basement optically-coupled.As herein describedly can also make a rigid basement have interim or lasting re-binding with respect to other rigid basement from supporting adhesive, this is by peeling off one or two rigid basement to realize from supporting adhesive from as herein described.
Fig. 2 is the schematic cross sectional views of another exemplary optical article 200.Optical goods 200 comprise first rigid optical substrate 210, second rigid optical substrate 220 and be arranged on first rigid basement 210 and second rigid basement 220 between the optical adhesive of supporting certainly 230.Comprise based on the polymer network of crosslinking silicone and be at least partially disposed on silicone liquid in the polymer network from supporting optical adhesive 230, as mentioned above.
Optical thin film 240 (or the 3rd rigid basement 240) is arranged on certainly and supports on the optical adhesive 230, and second optical adhesive 250 is arranged on the optical thin film 240.In a plurality of embodiment, second optical adhesive 250 is to solidify or crosslinkedly be the construction adhesive of lasting binding agent, and this construction adhesive is fixed to optical thin film 240 on first rigid optical substrate 210.In other embodiments, second optical adhesive 250 is a contact adhesive, it is adhered to optical thin film 240 on first rigid optical substrate 210 to be adhered to the stronger bonding strength of bonding strength on second rigid basement 220 than supporting optical adhesive 230 certainly.
In many optical display applications, first rigid optical substrate 210 (such as (for example) touch-screen or other sensor panels or protecting cover) can remove from second rigid basement 220 (such as (for example) panel of LCD or unit), and replaces with first rigid optical substrate, 210 substitutes (such as (for example) touch-screen or other sensor panels or protecting cover).
In one exemplary embodiment, as herein describedly be used in the panel computer from supporting adhesive, this panel computer can comprise, for example, panel of LCD and overlay on protecting cover on clear sensor layer, panel of LCD and/or the LCD on the LCD perhaps is covered with the panel of LCD of clear sensor layer and is positioned at protecting cover on this clear sensor panel on it.Panel computer be provided with usually can with the interactional active or passive stylus of alignment sensor, this alignment sensor can be arranged on the top of LCD or below.When below sensor element is arranged on LCD, can above LCD, provide transparent cover to avoid damaging with the protection LCD.When sensor element is transparent lcd overlay, no matter this clear sensor itself still independent cover layer can provide protection for LCD.As required, as herein describedly can be arranged between any of these rigid optical substrate from supporting adhesive, and can allow relatively easily to remove clear sensor panel and/or protecting cover.For example, if the coating sensor panel breaks down, if or sensor coating or protecting cover excessively scratched or damaged, can only replace sensor panel or protecting cover so, this is because as herein describedly have lasting re-binding from supporting the rigid optical element that adhesive allows to adhere to.
In a plurality of embodiment, the haze value that optical goods as herein described have can for 15% or lower, 10% or lower, 5% or lower, 3% or lower or 1% or lower, or 0 to 1%.In a plurality of embodiment, the visible light transmittance rate that optical goods as herein described have can 70% or bigger, 80% or bigger, 90% or bigger or 95% or bigger scope in.Mist degree and visible light transmittance rate value can be measured like that according to following " method of testing " part is defined.
Optical thin film can be any material with above-mentioned optical characteristics.In certain embodiments, optical substrate can be any polymeric material.The part tabulation of these polymer comprises (for example) polyolefin, polyacrylate, polyester, Merlon, fluoropolymer etc.Can be with one or more polymer combinations to form polymeric optical film.
It is in certain embodiments, as herein described that supporting adhesive can comprise that at least one has the first type surface of smooth surface certainly.In other embodiments, adhesive can be such layer, and this layer has at least one first type surface that has structured topography.Micro-structural on the adhesive layer surface can have specific shape, and this shape allows laminated or the air at the interface or other fluids that are entrained in from supporting between adhesive and the rigid basement are discharged.
Micro-structural on the adhesive phase (and the corresponding micro-structural on the release liner) can be a microcosmic on two dimensions at least.The dimension that human eye is difficult to differentiate when this used term " microcosmic " is meant not by microscope.A useable definition of microcosmic is that wherein visual acuity is to define and measure according to the angle square of the minimum character that can be recognized is very little.Normal visual acuity allows to differentiate the character of the angle height that divides facing to 5 arcs on the retina.
Can be from the micro-structural of supporting in the adhesive phase according to U.S. Patent No. 5,268,228, No.6,197,397 and No.6, be prepared described in 123,890, these patents are incorporated this paper into way of reference separately.Can pass through any contact technique (for example, cast, coating, embossing or compression) and in adhesive phase, produce this surface characteristics.Surface characteristics can be by at least a the making in the following method: (1) is cast in adhesive phase on the instrument with imprinted pattern; (2) adhesive phase is coated on the release liner with imprinted pattern; Or (3) make adhesive phase pass roll, so that adhesive is pressed against on the release liner with imprinted pattern.Can use any known technology such as for example chemical etching, mechanical etching, laser ablation, photoetching, stereolithography, little processing, annular knurl, cutting or line to prepare the surface characteristics that instrument had that is used to form imprinted pattern.
Liner can be arranged on certainly and support on adhesive phase or the micro-structural adhesive phase, and can be known any release liner of those skilled in the art or transfer liner, and these liners can impress as stated above in some cases.Liner can be according to placing with the mode that adhesive closely contacts, and remove subsequently and can not damage adhesive phase.The limiting examples of liner comprises and derives from 3MCompany (St.Paul, Minn.), Loparex (Willowbrook Ill.), P.SSubstrates, Inc., Schoeller Technical Papers, the material of Inc., AssiDomanInncoat GMBH and P.W.A.Kunstoff GMBH.Liner can be the poly-coated paper that has barrier coat, PETG (PET) film that has the coating polyethylene of barrier coat or the casting polyolefine film that has barrier coat.Adhesive phase and/or release liner can randomly comprise other non-sticky micro-structural, such as (for example) U.S. Patent No. 5,296,277, No.5, and 362,516 and No.5, those described in 141,790.These micro-structural adhesive phases with non-sticky micro-structural can trade name CONTROLTAC PLUS
TMDerive from 3MCompany (St.Paul, Minn.).
Micro-structural can formation rule or irregular array or pattern.The array or the pattern of rule comprise (for example) straight-line pattern, polarity pattern, right-angled intersection pattern or cube-corner patterns.Pattern can be arranged along the direction of carrier tablet, or can be with respect to the angled arrangement of carrier tablet.Micro structured pattern is positioned on two opposing first type surfaces of adhesive phase alternatively.This makes and can control with the surf zone that contacts the situation that flows out of each surperficial air in two surfaces respectively, to regulate the character of this adhesive at two different interfaces.
Micro structured pattern can limit continuous basically open channel or the groove that extends into adhesive phase from exposed surface.Passage can stop at the peripheral part that supports adhesive phase certainly, and perhaps other passages that can stop with the peripheral part at goods communicate.When supporting adhesive phase and be coated on the rigid optical substrate, the fluid at the interface that this passage allows to be entrained in from supporting between adhesive phase and the rigid optical substrate flows out with micro-structural.
Degree that the shape of micro-structural can flow out with the required fluid of concrete application in the adhesive phase and peel adhesion and along with the surface property of substrate great changes will take place.Can adopt the structure of projection and depression, and this micro-structural can be continuous in to form groove in adhesive phase.The method that is easy to get of considering pattern density, binder performance and being used to prepare micro-structural, suitable shape comprise hemisphere, right pyramid, trigonal pyramid, positive rectangular pyramid, tetragonal pyramid and " V " type groove.Micro-structural can systematically or randomly generate.
Not will be understood that the present invention is confined to instantiation mentioned above, on the contrary, should be appreciated that the various aspects of the present invention that the present invention is contained in the appended claims to be set forth.For the technical staff of the technical field of the invention, after reading this specification, various modification, the equivalent processes that the present invention can carry out and to can be applicable to many structures of the present invention will be conspicuous.
Example
These examples are only used for illustrative purpose, and are not the scope that is intended to limit appended claims.Except as otherwise noted, otherwise all umbers in example and the specification remainder, percentage, ratio etc. all by weight.Except as otherwise noted, otherwise used solvent and other reagent all derive from SIGMA Alder Ritchie (the Sigma-AldrichChemical Company of chemical company in Milwaukee, state of Wisconsin city; Milwaukee, Wisconsin).
The abbreviation table
| Abbreviation or trade name | Explanation |
| Additive-treated oil | RHODORSIL liquid 47V1,000 (RHODORSIL Fluid 47 V1,000), medium-viscosity (1000cps, straight chain dimethyl silicone polymer liquid 1.0Pas), can from Rhodia Silicones (S.A.S., Lyon, France) commercially available. |
| Crosslinking additives | PERKADOX PD-50S-PS-A, the peroxidating 2 in silicone oil, the 4-dichloro-benzoyl, can from Akzo Nobel Polymer Chemicals LLC (Chicago, IL) commercially available. |
| PDMS diamines 33,000 | PDMS, its molecular weight are about 33,000, according to U.S. Patent No. 5,461, and the preparation of method described in 134 the example 2. |
| DYTEK A | Organic diamine, can from DuPont (Wilmington, DE) commercially available. |
| H12MDI | Desmodur W, di-2-ethylhexylphosphine oxide cyclohexylene-4,4 '-vulcabond, can from Bayer (Pittsburgh, PA) commercially available. |
| The PETG of priming | Apply the polyester film of the PETG type of amination polybutadiene priming paint, thickness is 38 microns. |
| Unprimed PETG | The polyester film of unprimed PETG type, thickness are 50 microns or 125 microns. |
| 33K MAUS | Methacryloxy urea siloxanes, according to U.S. Patent No. 5,514, described in 730 the 14th hurdles, as to use 33,000 preparations of PDMS diamines a kind of difunctional siloxane acrylate at 35K MAUS. |
| IOA | Isooctyl acrylate monomer |
| DAROCUR 1173 | Light trigger: 2-hydroxy-2-methyl-1-phenyl third-1-ketone, derive from CibaSpecialty Chemicals (Hawthorne, NY). |
| PDMS diamines 5,000 | PDMS, its mean molecule quantity are about 5,000 gram/moles, according to U.S. Patent No. 5,214, and the preparation of method described in 119. |
| EDA | 1, the 2-ethylenediamine |
| HDA | 1, the 6-hexamethylene diamine |
| XDA | M-xylene diamine |
Method of testing
Transmittance (visible transmission ratio), mist degree and transparency
According to the method for testing D 1003-95 of American Society Testing and Materials (ASTM) (" StandardTest for Haze and Luminous Transmittance of TransparentPlastic "), use derives from BYK-GardnerInc., and (Silver Springs, TCS Plus spectrophotometer Md.) (TCS Plus Spectrophotometer) is measured the transmittance and the mist degree of all samples.Use the transmission and the reflectance spectrum of Perkin-Elmer Lambda 9 spectrophotometric determination samples.Laminated thing is tested, and this laminated thing is prepared by the adhesive sample between PETG (50 microns) and the glass.Also use identical instrument and laminated thing to measure transparency.
180 ° of peel adhesion
The method of testing of describing among this peel adhesion test and the ASTM D 3330-90 is similar, substitutes the stainless steel-based end described in this test with substrate of glass.
Adhesive coating on the polyester film is cut into the band of 15 centimetres of 1.27 cm x.Then, by once each band being adhered to 10 centimetres takes advantage of on 20 centimetres the clean glass specimen piece of crossing with solvent wash with the spreading on band of 2 kilograms roller.The assembly of bonding was at room temperature preserved for 1 week or 1 week of preservation under 70 ℃.Use IMASS test machine (the Model 3M90 that slides/peel off, can from Instrumentors Inc. (Strongsvil le, OH) commercially available) with the speed of 2.3 meters/minute (90 inch per minute clocks) through 5 second data collection time come 180 ° of peel adhesion of specimen.Test two samples, the peel adhesion value that is write down is the mean value from two samples peel adhesion value separately.Data are that newton/decimetre (N/dm) is collected and converted in unit with gram/inch (g/in).
The wetting speed test
Whether the sample that is coated on the PETG of priming of test is convenient to laminated in the following manner: sample layer is incorporated on the substrate of glass, observes wetting rate and with 1 to 5 grade wetting speed is graded.Rank " 1 " is minimum wetting rate, and rank " 5 " is the highest wetting rate.
Rigidity-rigid lamination wet situation test
The laminated process of glass-glass at multilayer layer compound form is tested the adhesive sample that is coated on the PETG of priming.With optically transparent, the transfering adhesive of two liners (the optically transparent laminating adhesive 8141 of 3M (3M Optically Clear LaminatingAdhesive 8141), can be from (the St.Paul of 3M company, MN) commercially available) be laminated to the PETG side of priming in the sample arrangement of PETG of unprimed PETG liner/example adhesive/prime, to form following structure: the PETG/example adhesive/unprimed PETG liner of transfering adhesive liner/transfering adhesive/prime.The transfering adhesive liner is removed, and this techonosphere is incorporated into area is that 7.6 centimetres of 5.0 cm x (2 inches * 3 inches), thickness are on 1 millimeter the slide.Unprimed PETG liner is removed, and example adhesive is placed on area is that 20 centimetres of 15 cm x (6 inches * 8 inches), thickness are on 1 millimeter the sheet glass.This constructs finger of no use to pressing down or coming laminated with roller.Make example adhesive wetting and laminated automatically under the gravity effect.If wettingly spontaneously begin, the rigidity of this sample-rigid lamination wet situation is rated as "Yes" so.If do not begin in 1 minute wetting, so with finger with one side of slide to pressing down in the hope of producing wetting cutting edge of a knife or a sword.If at this moment begin wettingly, the rigidity of this sample-rigid lamination wet situation is rated as "Yes" so.If after 5 minutes seldom wetting or do not take place wetting, even after finger pressure being applied on one side of slide still so, the rigidity of this sample-rigid lamination wet situation is rated as "No" so.Wettingly begin if observe, but owing to dust granule, coating layer thickness change or other abnormal factorses interrupt, the rigidity of this sample-rigid lamination wet situation is rated as "Yes" so.
Preparation property example 1: silicone polyurea (SPU) is elastomeric synthetic
In reaction vessel, PDMS diamines 33,000, DYTEK A, H12MDI are placed in enough 2-propyl alcohol with the mol ratio of 1:1:2, so that the solution of 20% solid to be provided.The mixture of stirring gained 2 hours is to provide the silicone polyurea elastomer.
Preparation property example 2: silicone polyoxamide elastomers precursor synthetic
Diethy-aceto oxalate (241.10 gram) put in 3 mouthfuls of resin flask of 3 liters, described flask is equipped with mechanical agitator, heating jacket, nitrogen inlet tube (band stopcock) and outlet.With nitrogen flask was purged 15 minutes, and under agitation slowly add PDMS diamines 5,000 (2,028.40 grams, molecular weight equals 4,918 gram/moles).After following 8 hours of the room temperature, reaction flask is mixed distillation adapter and receiver.Stir content and be heated to 150 ℃ down in vacuum (133 handkerchiefs, 1 holder), continue 4 hours, until no longer collecting distillate.Remaining liq is cooled to room temperature, obtains 2,573 grams.The gas chromatographic analysis of the mobile liquid of clarification shows, but do not have the diethy-aceto oxalate of detection limit.Use
1H NMR comes determining molecular weight (molecular weight equals 5,477 gram/moles), and comes determining molecular weight (equivalent weight of two titration samples is respectively 2,722 gram/equivalents and 2,721 gram/equivalents) by titration.
Preparation property example 3: silicone polyoxamide HDA is elastomeric synthetic
The precursor (793.20 gram) that preparation property example 2 is obtained is put in 3 mouthfuls of resin flask of 3 liters, and described flask is equipped with mechanical agitator, heating jacket, nitrogen inlet tube (band stopcock) and outlet.With nitrogen flask was purged 15 minutes, add HDA (17.48 gram) then.This mixture of mechanical agitation and be heated to 150 ℃ under nitrogen atmosphere continues 3.5 hours.Pour into the melting product of viscosity in the glass pallet and make its cooling, solid product is dissolved among the THF (1,620 gram).
Preparation property example 4: silicone polyoxamide EDA is elastomeric synthetic
The precursor (100.00 gram) that preparation property example 2 obtains is put into wide-mouth bottle.Add EDA (1.0243 gram).With wide-mouth bottle sealing, and stir the mixture fast, become too thickness and can't flow until content.After the standing over night, solid product is dissolved among the THF (200 gram) at ambient temperature.
Preparation property example 5: silicone polyoxamide XDA is elastomeric synthetic
Precursor (100.00 gram) and XDA (2.32 gram) that preparation property example 2 is obtained are metered in the wide-mouth bottle.With wide-mouth bottle sealing, and stir the mixture fast, become too thickness and can't flow until content.At ambient temperature, wide-mouth bottle is placed on the roller mill spends the night.Solid product is dissolved among the THF (200 gram).
Example 1-3 and comparative example C1
For example 1-3, prepare the silicone polyurea elastomeric adhesive: use conventional solvent device with the content blend of the silicone polyurea elastomer of above-mentioned preparation and additive-treated oil and crosslinking additives with 20% solid by following manner.For comparative example C1, do not use additive-treated oil or crosslinking additives.These samples are coated to by solvent mixture on the PETG of priming, are dried to 25 micron thickness and as described in Table 1 being cured then.In room temperature or after 1 week of wearing out for 70 ℃ times, according to above-mentioned method of testing sample is carried out 180 ° and peel off test.These data are summarised in the table 2.Also use above-mentioned wetting speed and rigidity-rigid lamination wet test that sample is tested, its data are shown in Table 2.For example 2, use above-mentioned method of testing to measure transmittance, mist degree and transparency, its data are shown in Table 6.
Table 1
| Example | Condition of cure | SPU elastomer (weight %) | Additive-treated oil (weight %) | Crosslinking additives (weight %) |
| 1 | 80 ℃ solidified 8 hours down | 59.5 | 40 | 0.5 |
| 2 | 120 ℃ solidified 5 minutes down | 59.5 | 40 | 0.5 |
| 3 | 150 ℃ solidified 6 minutes down | 59.5 | 40 | 0.5 |
| C1 | Drying is 30 minutes under 90 ℃ | 100 | 0 | 0 |
Table 2
| Example | 180 ° of peel adhesion (N/dm) under the room temperature after 1 week | 180 ° of peel adhesion (N/dm) after 70 ℃ of following 1 weeks | Wetting speed | Rigidity-rigid lamination wet situation |
| 1 | 0.385 | 0.963 | 5 | Be |
| 2 | 1.39 | 0.878 | 5 | NT |
| 3 | 1.39 | 0.785 | 5 | NT |
| C1 | 2.57 | 15.15 | 1 | Not |
NT=does not test
Example 4-5 and comparative example C2-C3
For example 4-5 and comparative example C2-C3, prepare the siloxanes acrylic ester adhesive as follows: with the DAROCUR1173 blend of 33K MAUS, IOA and additive-treated oil with ratio shown in the table 3 and 1 weight %.The sample of these prescriptions is coated on the pet film of priming, and covers, under 350nm low-intensity ultraviolet light, solidified 15 minutes then with unprimed pet film (as release liner).According to the test of carrying out wetting speed and rigidity-rigid lamination wet situation described in above-mentioned " method of testing ".Data are summarised in the table 3.
Table 3
| Example | 33K MAUS (weight %) | IOA (weight %) | Additive-treated oil (weight %) | Wetting speed | Rigidity-rigid lamination wet situation |
| 4 | 39.5 | 39.5 | 20 | 5 | Be |
| 5 | 34.5 | 34.5 | 30 | 5 | Be |
| C2 | 49.5 | 49.5 | 0 | 5 | Not |
| C3 | 44.5 | 44.5 | 10 | 5 | Not |
Example 6-8
For example 6-8, prepare the silicone polyoxamide elastomers adhesive: use the conventional solvent device will be by the content blend of the silicone polyoxamide elastomers for preparing described in the above-mentioned preparation example and additive-treated oil and crosslinking additives with 20% solid by following manner.For example 6, silicone polyoxamide elastomers is the HDA elastomer of preparation in the preparation property example 3, for example 7, silicone polyoxamide elastomers is the EDA elastomer of preparation in the preparation property example 4, for example 8, silicone polyoxamide elastomers is the XDA elastomer of preparation in the preparation property example 5.These samples are coated to by solvent mixture on the PETG of priming, are dried to 25 micron thickness and as described in Table 4 being cured then.In room temperature or after 70 ℃ times aging 3 days, according to above-mentioned method of testing sample is carried out 180 ° and peel off test.These data are summarised in the table 5.Also use above-mentioned wetting speed test that sample is tested, its data are shown in Table 5.Use above-mentioned method of testing to measure transmittance, mist degree and transparency, its data are shown in Table 6.
Table 4
| Example | Condition of cure | Silicone polyoxamide elastomers (weight %) | Additive-treated oil (weight %) | Crosslinking additives (weight %) |
| 6 | 120 ℃ solidified 5 minutes down | 59.5 | 40 | 0.5 |
| 7 | 120 ℃ solidified 5 minutes down | 59.5 | 40 | 0.5 |
| 8 | 120 ℃ solidified 5 minutes down | 59.5 | 40 | 0.5 |
Table 5
| Example | The 180 ° peel adhesion (N/dm) of room temperature after following 3 days | 70 ℃ of 180 ° of peel adhesion (N/dm) after following 3 days | Wetting speed |
| 6 | 6.77 | 1.54 | 5 |
| 7 | 1.39 | 9.76 | 5 |
| 8 | 1.39 | 2.85 | 5 |
Table 6
| Example | Average light transmittance (%) | Average mist degree (%) | Average transparency (%) |
| 2 | 91.43 | 2.44 | 99.3 |
| 6 | 91.17 | 5.95 | 99.1 |
| 7 | 91.20 | 4.32 | 99.3 |
| 8 | 91.00 | 4.78 | 99.3 |
Example 9
For example 9, prepare the siloxanes acrylic ester adhesive as follows: use the prescription identical, with DAROCUR 1173 blend of 33K MAUS, IOA and additive-treated oil with ratio shown in the table 7 and 1 weight % with comparative example C3.The sample of this prescription is coated on the pet film of priming, and covers, under 350nm low-intensity ultraviolet light, solidified 15 minutes then with unprimed pet film (as release liner).Test the wetting speed of this sample.Its data are shown in Table 7.Carry out improved rigidity-rigid lamination wet situation test, wherein use the thin layer of additive-treated oil to want laminated glass plate to carry out preliminary treatment example adhesive.Apply additive-treated oil by additive-treated oil being coated with put straticulation on the skin and scrape off unnecessary oil to form uniform shallow layer with razor blade.Data are summarised in the table 7.
Table 7
| Example | 33K MAUS (weight %) | IOA (weight %) | Additive-treated oil (weight %) | Wetting speed | Rigidity-rigid lamination wet situation |
| C3 | 44.5 | 44.5 | 10 | 5 | Not |
| 9 | 44.5 | 44.5 | 10 | 5 | Be |
* use the wetting situation test of improved rigidity-rigidity
Claims (20)
1. optical goods comprise:
First rigid optical substrate;
Second rigid optical substrate; And
Be arranged on the optical adhesive of supporting certainly between described first rigid basement and described second rigid basement, describedly comprise based on the polymer network of crosslinking silicone and be arranged on silicone liquid in the described polymer network from supporting optical adhesive.
2. optical goods according to claim 1, wherein said polymer network based on crosslinking silicone comprises the silicone polyurea elastomer.
3. optical goods according to claim 1, wherein said polymer network based on crosslinking silicone comprises silicone polyacrylates.
4. optical goods according to claim 1, wherein said polymer network based on crosslinking silicone comprises silicone polyoxamide elastomers.
5. optical goods according to claim 1, wherein said is 20 weight % to 50 weight % from supporting the silicone liquid that optical adhesive comprises.
6. optical goods according to claim 1, wherein said is 50 weight % to 80 weight % from supporting the silicone elastomer that optical adhesive comprises.
7. optical goods according to claim 1, wherein said first rigid optical substrate and described second rigid optical substrate comprise glass or quartz.
8. optical goods according to claim 1, wherein when measuring according to ASTM method of testing D1003-95, the haze value of described optical goods is less than 5%, and the visible transmission ratio is 90% or higher.
9. optical goods according to claim 1, wherein saidly be arranged on first side of optical thin film from supporting optical adhesive, and second optical adhesive is arranged on second side of described optical thin film, and described second side and described first side of wherein said optical thin film are opposing.
10. optical goods according to claim 9, wherein said oneself supports the optical adhesive that optical adhesive is lasting re-binding, and described second optical adhesive is a construction adhesive.
11. optical goods according to claim 1, wherein said second rigid optical substrate forms at least a portion of panel of LCD.
12. optical goods according to claim 1, wherein said first rigid optical substrate forms at least a portion of clear sensor panel.
13. optical goods according to claim 1, wherein said first rigid optical substrate forms at least a portion of clear sensor panel, and described second rigid optical substrate forms at least a portion of panel of LCD.
14. a method that forms optical goods, described method comprises:
First rigid optical substrate is provided, it has the optical adhesive layer of supporting certainly that surface and contiguous described surface are provided with, and describedly comprises based on the polymer network of crosslinking silicone and is arranged on silicone liquid in the described polymer network from supporting optical adhesive; And
Second rigid basement is laminated in described from supporting on the optical adhesive layer forming optical goods, wherein saidly is arranged between described first rigid optical substrate and described second optical substrate from supporting optical adhesive layer.
15. method according to claim 14, wherein saidly provide step also to comprise to be arranged on described from supporting the optical thin film on the optical adhesive layer and being arranged on opposing lip-deep second optical adhesive layer of described optical thin film, wherein said second optical adhesive is arranged between described optical thin film and described first rigid basement.
16. method according to claim 14, wherein said laminated step comprises: second rigid basement that will comprise panel of LCD is laminated to described from supporting on the optical adhesive layer, to form optical goods.
17. method according to claim 14, the wherein said step that provides comprises: first rigid optical substrate that comprises the clear sensor panel is provided.
18. method according to claim 14 also comprises described first rigid basement and describedly peels off from described second rigid basement from supporting optical adhesive layer.
19. method according to claim 18, also comprise the first rigid optical substrate substitute is provided, the described first rigid optical substrate substitute has the optical adhesive layer of supporting certainly of surface and the setting of contiguous described surface, describedly comprise based on the polymer network of crosslinking silicone and be arranged on silicone liquid in the described polymer network from supporting optical adhesive, then described second rigid basement is laminated on the optical adhesive layer of supporting certainly of the described first rigid optical substrate substitute, to form the optical goods of repairing, the optical adhesive layer of supporting certainly of the wherein said first rigid optical substrate substitute is arranged between described first rigid optical substrate substitute and described second optical substrate.
20. method according to claim 14 wherein saidly provides step also to comprise the optical adhesive layer of the supporting certainly with micro-structural adhesive surface is provided.
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| Application Number | Priority Date | Filing Date | Title |
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| US11/426,844 | 2006-06-27 | ||
| US11/426,844 US7655283B2 (en) | 2006-06-27 | 2006-06-27 | Rigid optical laminates and methods of forming the same |
| PCT/US2007/071160 WO2008002772A1 (en) | 2006-06-27 | 2007-06-14 | Rigid optical laminates and methods of forming the same |
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| CN101479104B CN101479104B (en) | 2012-05-02 |
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| Country | Link |
|---|---|
| US (1) | US7655283B2 (en) |
| EP (1) | EP2035225B1 (en) |
| JP (1) | JP5180204B2 (en) |
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| US7258437B2 (en) * | 2005-09-07 | 2007-08-21 | Transitions Optical, Inc. | Photochromic multifocal optical article |
-
2006
- 2006-06-27 US US11/426,844 patent/US7655283B2/en active Active
-
2007
- 2007-06-14 EP EP07798529.9A patent/EP2035225B1/en not_active Not-in-force
- 2007-06-14 CN CN2007800241947A patent/CN101479104B/en not_active Expired - Fee Related
- 2007-06-14 JP JP2009518439A patent/JP5180204B2/en not_active Expired - Fee Related
- 2007-06-14 WO PCT/US2007/071160 patent/WO2008002772A1/en active Application Filing
- 2007-06-14 KR KR1020087031591A patent/KR101323499B1/en not_active IP Right Cessation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102648427A (en) * | 2009-12-08 | 2012-08-22 | 3M创新有限公司 | Optical constructions incorporating a light guide and low refrative index films |
| CN103085364A (en) * | 2011-10-28 | 2013-05-08 | 三星显示有限公司 | Windowfor display protection and display using the same |
| CN104823080A (en) * | 2012-07-26 | 2015-08-05 | 3M创新有限公司 | Heat de-bondable optical articles |
| CN111417519A (en) * | 2017-11-30 | 2020-07-14 | 3M创新有限公司 | Substrate comprising self-supporting three-layer stack |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101479104B (en) | 2012-05-02 |
| US20070297736A1 (en) | 2007-12-27 |
| JP5180204B2 (en) | 2013-04-10 |
| EP2035225A4 (en) | 2014-04-02 |
| EP2035225A1 (en) | 2009-03-18 |
| KR101323499B1 (en) | 2013-10-31 |
| EP2035225B1 (en) | 2015-08-26 |
| KR20090021362A (en) | 2009-03-03 |
| WO2008002772A1 (en) | 2008-01-03 |
| US7655283B2 (en) | 2010-02-02 |
| JP2009543132A (en) | 2009-12-03 |
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